雙功能三唑卡賓前驅(qū)體的合成及其在不對(duì)稱(chēng)硅基化中的應(yīng)用研究
發(fā)布時(shí)間：2018-08-07 09:18
【摘要】：在有機(jī)化學(xué)反應(yīng)研究中,催化形成新的化學(xué)鍵是非常重要的。催化劑可以使反應(yīng)進(jìn)行的更加容易,選擇性更好而且環(huán)境友好,使用高效的催化劑可以發(fā)展許多新的合成策略。同時(shí),將催化劑應(yīng)用于經(jīng)典反應(yīng)得到的結(jié)果往往讓人驚喜。而不對(duì)稱(chēng)催化更是催化研究的重中之重。卡賓類(lèi)催化劑是有機(jī)化學(xué)領(lǐng)域中研究最多的催化劑之一。從第一個(gè)卡賓催化劑合成以來(lái),卡賓被廣泛應(yīng)用于不對(duì)稱(chēng)催化反應(yīng)中。與膦配體和氮磷配體相比卡賓具有獨(dú)特的電子效應(yīng),可以應(yīng)用于有機(jī)金屬催化和有機(jī)催化反應(yīng)中。目前廣泛應(yīng)用的氮雜環(huán)卡賓催化劑是三氮唑卡賓。手性催化劑的特征是都包含至少一個(gè)手性元素,我們將帶有中心手性的卡賓引入[2.2]環(huán)仿中,得到了一類(lèi)新型雙手性配體。該配體可以與銅形成配合物催化反應(yīng),也可以單獨(dú)進(jìn)行有機(jī)催化,是一類(lèi)新型的兩用催化劑。我們課題組利用該類(lèi)配體催化不飽和羰基化合物的硼化反應(yīng)和硅基化反應(yīng)都得到了很好的結(jié)果。水是地球上最豐富的分子之一。它非常便宜,特別是與有機(jī)溶劑相比,水是不可燃和無(wú)毒的,而且具有大的熱容量,所以如果適當(dāng)使用水作為有機(jī)反應(yīng)溶劑可帶來(lái)許多環(huán)境益處和意想不到的結(jié)果。而我們以前合成的配體在水相中均不能進(jìn)行催化反應(yīng)。因此我們想嘗試對(duì)以前合成的三氮唑鹽進(jìn)行修飾,得到一種雙功能的新型三氮唑鹽,希望能將其應(yīng)用于水相不對(duì)稱(chēng)硅基化的反應(yīng)中。本論文包括以下幾部分內(nèi)容。1.對(duì)卡賓催化及卡賓在水相中的催化進(jìn)行歸納綜述自從穩(wěn)定的卡賓被Bertrand等人首次報(bào)道以來(lái),N-雜環(huán)卡賓(NHCs)在有機(jī)催化中的得到了非常廣泛的應(yīng)用。卡賓配體可以與過(guò)渡金屬結(jié)合催化許多反應(yīng),也可以進(jìn)行有機(jī)催化反應(yīng),其催化的反應(yīng)也從安息香縮合反應(yīng)等零星反應(yīng)到廣泛使用。有機(jī)反應(yīng)在水或水性介質(zhì)中進(jìn)行可以帶來(lái)許多益處,例如產(chǎn)物在水中的溶解度較低,更容易分離產(chǎn)物;水是更安全的反應(yīng)介質(zhì),可以降低成本等。2.雙功能三氮唑鹽的合成以拆分好的SP-4-氨基-12-溴[2.2]環(huán)仿為原料,通過(guò)重氮化反應(yīng)得到重氮鹽,再與LiBr反應(yīng)得到Sp-4,12-二溴[2.2]環(huán)仿。Sp-4,12-二溴[2.2]環(huán)仿與二苯酮腙反應(yīng)得到Sp-4-二苯酮腙-12-溴[2.2]環(huán)仿,然后通過(guò)加甲�；磻�(yīng)得到Sp-4-(N-甲�；酵昊�)-12-溴[2.2]環(huán)仿。上步產(chǎn)物與2-羥基苯硼酸反應(yīng)后,酸解得到SP-4-(N-甲酰肼基)-12-(2-苯酚基)[2,2]環(huán)仿鹽酸鹽,然后與S-叔丁基嗎啉酮亞胺醚反應(yīng)得到三唑鹽(S,Sp)-2。(S,Sp)-3的合成與上述步驟相同。3.雙功能三氮唑卡賓催化芳香醛的不對(duì)稱(chēng)硅基化反應(yīng)以DBU做堿,在水作溶劑的情況下,(S,Sp)-3可以催化芳香醛與硅試劑發(fā)生加成反應(yīng)。并在最有條件下對(duì)底物進(jìn)行了拓展,發(fā)現(xiàn)大多數(shù)的醛都可以得到高的收率和中等的er值。創(chuàng)新點(diǎn)1.我們合成了一系列新穎的基于[2.2]環(huán)仿的雙功能三氮唑卡賓前驅(qū)體,并在環(huán)仿上成功引入活性基團(tuán)。2.首次實(shí)現(xiàn)了水相中卡賓催化芳香醛的不對(duì)稱(chēng)硅基化反應(yīng),并取得了不錯(cuò)的收率和er值。
[Abstract]:In the study of organic chemical reactions, it is very important to catalyze the formation of new chemical bonds. The catalyst can make the reaction easier, more selective and environmentally friendly, and many new synthetic strategies can be developed using high efficient catalysts. At the same time, the results of the application of the catalyst to the classical reaction are often surprising. Symmetric catalysis is more important in catalytic research. CABBEEN catalyst is one of the most widely studied catalysts in the field of organic chemistry. Since the synthesis of the first CABBEEN catalyst, CABBEEN has been widely used in asymmetric catalytic reactions. Compared with phosphine ligands and nitrogen and phosphorus ligands, CABBEEN has a unique electronic effect and can be applied to organic gold. In the catalytic and organic catalytic reactions, the widely used nitrogen heterocyclic CABBEEN catalyst is three azoles CABBEEN. The chiral catalyst is characterized by at least one chiral element. We introduce a central chiral CABBEEN into the [2.2] cycle to obtain a new type of both hands. This ligand can catalyze the reaction of the ligand with copper. It is a new type of dual use catalyst. Our group uses this kind of ligand to catalyze the boronizing reaction and silicylation of unsaturated carbonyl compounds. Water is one of the richest molecules on earth. It is very cheap, especially when compared with organic solvents, water is not flammable. It is nontoxic and has large thermal capacity, so if proper use of water as an organic reaction solvent can bring many environmental benefits and unexpected results. And our previously synthesized ligands are not catalyzed in the aqueous phase. Therefore, we would like to try to modify the previously synthesized three azoles to get a double function. The new three azoles of three azoles are expected to be applied to the reaction of asymmetric silylation in aqueous phase. This paper includes the following parts of the summary of the following contents:.1. catalysis and the catalysis of CABBEEN in the water phase. Since the stable CABBEEN was first reported by Bertrand et al., the N- heterocyclic CABBEEN (NHCs) has been obtained in the organic catalysis A wide range of applications. CABBEEN ligands can catalyze many reactions with transition metals, as well as organic catalysis, and their catalytic reactions are also widely used from the benzoin condensation reaction to a wide range of use. Organic reactions can bring many benefits in water or aqueous media, such as low solubility in water and more capacitive products. The water is a more safe product; water is a more safe reaction medium, it can reduce the cost of.2. bifunctional three azoles, such as the synthesis of a good SP-4- amino -12- bromine [2.2] ring as raw material, the diazonium salt is obtained by the diazotization reaction, and the reaction of Sp-4,12- dibromine [2.2] ring like.Sp-4,12- dibrominated [2.2] ring and two benzophenone hydrazone reacts with LiBr to obtain Sp-4-. The two benzophenone hydrazone -12- bromine [2.2] ring is imitated, and then the Sp-4- (N- formyl two benzophenone hydrazone) -12- bromine [2.2] ring is obtained by the formylation reaction. After the reaction of the step product and 2- hydroxybenzboric acid, SP-4- (N- formyl hydrazine) -12- (2- phenol) [2,2] ring imitating hydrochloride is obtained, and then three azolium salts are reacted with tertiary butyl morpholone imide ether. (S, Sp) -3 synthesis and the same.3. double function three nitroazole CABBEEN catalyzes the asymmetric silicylation of aromatic aldehydes with DBU. In the case of water as solvent, (S, Sp) -3 can catalyze the addition reaction of aromatic aldehydes with silicon reagents. And the substrate is expanded under the most conditions, and most aldehydes can be obtained high. The yield and medium Er value. Innovation 1. we synthesized a series of novel double functional three azazole CABBEEN precursors based on [2.2], and successfully introduced the active group.2. in the cyclic imitation for the first time to realize the asymmetric silicylation of aromatic aldehyde catalyzed by CABBEEN in the water phase, and obtained a good yield and ER value.
【學(xué)位授予單位】：山東大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O621.251
[Abstract]:In the study of organic chemical reactions, it is very important to catalyze the formation of new chemical bonds. The catalyst can make the reaction easier, more selective and environmentally friendly, and many new synthetic strategies can be developed using high efficient catalysts. At the same time, the results of the application of the catalyst to the classical reaction are often surprising. Symmetric catalysis is more important in catalytic research. CABBEEN catalyst is one of the most widely studied catalysts in the field of organic chemistry. Since the synthesis of the first CABBEEN catalyst, CABBEEN has been widely used in asymmetric catalytic reactions. Compared with phosphine ligands and nitrogen and phosphorus ligands, CABBEEN has a unique electronic effect and can be applied to organic gold. In the catalytic and organic catalytic reactions, the widely used nitrogen heterocyclic CABBEEN catalyst is three azoles CABBEEN. The chiral catalyst is characterized by at least one chiral element. We introduce a central chiral CABBEEN into the [2.2] cycle to obtain a new type of both hands. This ligand can catalyze the reaction of the ligand with copper. It is a new type of dual use catalyst. Our group uses this kind of ligand to catalyze the boronizing reaction and silicylation of unsaturated carbonyl compounds. Water is one of the richest molecules on earth. It is very cheap, especially when compared with organic solvents, water is not flammable. It is nontoxic and has large thermal capacity, so if proper use of water as an organic reaction solvent can bring many environmental benefits and unexpected results. And our previously synthesized ligands are not catalyzed in the aqueous phase. Therefore, we would like to try to modify the previously synthesized three azoles to get a double function. The new three azoles of three azoles are expected to be applied to the reaction of asymmetric silylation in aqueous phase. This paper includes the following parts of the summary of the following contents:.1. catalysis and the catalysis of CABBEEN in the water phase. Since the stable CABBEEN was first reported by Bertrand et al., the N- heterocyclic CABBEEN (NHCs) has been obtained in the organic catalysis A wide range of applications. CABBEEN ligands can catalyze many reactions with transition metals, as well as organic catalysis, and their catalytic reactions are also widely used from the benzoin condensation reaction to a wide range of use. Organic reactions can bring many benefits in water or aqueous media, such as low solubility in water and more capacitive products. The water is a more safe product; water is a more safe reaction medium, it can reduce the cost of.2. bifunctional three azoles, such as the synthesis of a good SP-4- amino -12- bromine [2.2] ring as raw material, the diazonium salt is obtained by the diazotization reaction, and the reaction of Sp-4,12- dibromine [2.2] ring like.Sp-4,12- dibrominated [2.2] ring and two benzophenone hydrazone reacts with LiBr to obtain Sp-4-. The two benzophenone hydrazone -12- bromine [2.2] ring is imitated, and then the Sp-4- (N- formyl two benzophenone hydrazone) -12- bromine [2.2] ring is obtained by the formylation reaction. After the reaction of the step product and 2- hydroxybenzboric acid, SP-4- (N- formyl hydrazine) -12- (2- phenol) [2,2] ring imitating hydrochloride is obtained, and then three azolium salts are reacted with tertiary butyl morpholone imide ether. (S, Sp) -3 synthesis and the same.3. double function three nitroazole CABBEEN catalyzes the asymmetric silicylation of aromatic aldehydes with DBU. In the case of water as solvent, (S, Sp) -3 can catalyze the addition reaction of aromatic aldehydes with silicon reagents. And the substrate is expanded under the most conditions, and most aldehydes can be obtained high. The yield and medium Er value. Innovation 1. we synthesized a series of novel double functional three azazole CABBEEN precursors based on [2.2], and successfully introduced the active group.2. in the cyclic imitation for the first time to realize the asymmetric silicylation of aromatic aldehyde catalyzed by CABBEEN in the water phase, and obtained a good yield and ER value.
【學(xué)位授予單位】：山東大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O621.251
【相似文獻(xiàn)】
相關(guān)期刊論文 前10條
1 蔣錫夔;;卡賓的化學(xué)[J];化學(xué)通報(bào);1962年07期
2 蔣錫夔;;卡賓化學(xué)的進(jìn)展及某些問(wèn)題[J];科學(xué)通報(bào);1965年08期
3 張必良;;卡賓化學(xué)分支——高張力環(huán)卡賓的進(jìn)展[J];化學(xué)通報(bào);1987年11期
4 馬艷鳳,馬楠,孟繁友;關(guān)于卡賓的研究[J];松遼學(xué)刊(自然科學(xué)版);1997年03期
5 孫小宇;吳R，
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